In order to further study the corrosion mechanism of acidizing corrosion inhibitor，the relationship between molecular structure and inhibition efficiency of corrosion inhibitor was analyzed by combining experimental method with quantum chemistry and molecular dynamics. The inhibition efficiency of five acidizing corrosion inhibitors in 15% HCl solution was measured by weight loss method，such as glycine，N-［N-［（phenylmethoxy）carbonyl］glycyl］-，4-nitrophenyl ester（A），Nα，ω-dicarbobenzoxy-L-arginine （B），N-（2-benzoylphenyl）-1-benzylpyrrolidine-2-carboxamide（C），ethyl（E）-3-（4-（（（E）-4-methoxybenzylidene）amino）phenyl） acrylate（D），2-amino-3-（5-hydroxy-1H-indol-3-yl propanoic acid（E）. And the 3D morphology of N80 steel after corrosion was observed by metallographic microscope. Finally，the corrosion inhibition performance of five corrosion inhibitors was analyzed by the combination of quantum mechanics and molecular dynamics. The results showed that the inhibition efficiency of five acidizing corrosion inhibitors was above 93%. The inhibition effects of five acidizing corrosion inhibitors were arranged according to the order of inhibition efficiency in following order：B>A>D>C>E，according to average pitting depth in following order：B>A>D>C>E，and according to maximum pitting depth in following order：A>B>D>C>E. B and D corrosion inhibitor had poor inhibitory effect of pitting corrosion. The corrosion inhibition performances of five corrosion inhibitors were arranged according to the calculated results by quantum chemistry in following order：A>B>D>C>E，and according to the calculated results by molecular mechanics in following order：A>B>C>D>E，which agreed with the experimental results.